CN111856878B

CN111856878B - Resist underlayer composition and method for forming pattern using the same

Info

Publication number: CN111856878B
Application number: CN202010267952.5A
Authority: CN
Inventors: J·凯茨; K·杨; 张可人; J·F·卡梅伦; 崔莉; E·阿卡德; 山田晋太郎; P·J·拉博姆
Original assignee: Rohm and Haas Electronic Materials LLC
Current assignee: Rohm and Haas Electronic Materials LLC
Priority date: 2019-04-30
Filing date: 2020-04-07
Publication date: 2024-04-12
Anticipated expiration: 2040-04-07
Also published as: TWI757715B; KR102414900B1; US20200348592A1; CN111856878A; JP2020184067A; JP7003176B2; KR20200126903A; TW202104426A

Abstract

A resist underlayer composition comprising a poly (arylene ether), an additive polymer different from the poly (arylene ether), and a solvent, wherein the additive polymer comprises aromatic or heteroaromatic groups having at least one protected or free functional group selected from hydroxyl, mercapto, and/or amino groups.

Description

Resist underlayer composition and method for forming pattern using the same

Technical Field

The present disclosure relates to spin-on carbon compositions for use as etch masks for photolithography in the semiconductor industry. In particular, the present disclosure relates to resist underlayer compositions having enhanced substrate adhesion.

Background

Spin-on carbon (SOC) compositions are used in the semiconductor industry as etch masks for photolithography in advanced technology nodes of integrated circuit fabrication. These compositions are typically used in three-layer and four-layer photoresist integration schemes, where an organic or silicon-containing antireflective coating and a patternable photoresist film layer are disposed on a bottom layer having a high carbon content SOC material.

The ideal SOC material should have certain specific characteristics: it should be capable of being cast onto a substrate by spin coating processes, should be thermally cured upon heating, have low outgassing and sublimation, should be soluble in common solvents to have good spin-drum compatibility (spin bowl compatibility), should have a suitable n/k to work with anti-reflective coatings to impart the low reflectivity required for photoresist imaging, and should have high thermal stability to avoid damage during subsequent processing steps. In addition to these requirements, the ideal SOC material must provide a flat film when spin-coated and thermally cured on the substrate that has a topography and sufficient dry etch selectivity to the silicon-containing layers above and below the SOC film to transfer the light pattern into the final substrate in a precise manner.

Organic polyarylene has been used to provide semiconductors with low dielectric constants. Polyarylene is also used as an SOC material patterned in a three or four layer process. Such polyarylene SOC formulations can have high thermal stability, high etch resistance, and good planarization under test conditions. However, the adhesion of conventional polyarylene substrates to inorganic substrates is limited and may cause problems in some processing steps. For example, during removal of the substrate by wet chemical etching, conventional polyarylene formulations delaminate from the substrate, resulting in an unacceptable loss of pattern fidelity and substrate damage.

There remains a need for new SOC materials with improved adhesion properties.

Disclosure of Invention

A resist underlayer composition is provided herein. The composition includes a poly (arylene ether), an additive polymer other than a poly (arylene ether), and a solvent. The additive polymer comprises an aromatic or heteroaromatic group having at least one protected or free functional group selected from hydroxyl, mercapto and amino groups.

A method of forming a pattern is also provided herein. According to the method, a resist underlayer composition layer is applied on a substrate. The applied resist underlayer composition is then cured to form a resist underlayer. A photoresist layer is then formed over the resist underlayer.

Detailed Description

Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. In this regard, the present exemplary embodiment may have different forms and should not be construed as limited to the description shown herein. Accordingly, only exemplary embodiments are described below to explain various aspects of the inventive concept. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. When a statement such as "at least one/each of the list of elements" precedes the list of elements, it modifies the entire list of elements and does not modify individual elements in the list.

It will be understood that when an element is referred to as being "on" another element, it can be directly in contact with the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.

It will be understood that, although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the present embodiment.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

It will be further understood that the terms "comprises" and/or "comprising," or "includes" and/or "including" when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.

Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

As used herein, the term "alkyl" refers to a group derived from a straight or branched chain saturated aliphatic hydrocarbon having the indicated number of carbon atoms and having a valence of at least 1.

As used herein, the term "alkenyl" refers to a group derived from a straight or branched chain unsaturated aliphatic hydrocarbon that includes at least one double bond, has the indicated number of carbon atoms, and has a valence of at least 1.

As used herein, the term "alkynyl" refers to a group derived from a straight or branched chain unsaturated aliphatic hydrocarbon that includes at least one triple bond, has the indicated number of carbon atoms, and has a valence of at least 1.

As used herein, the term "cycloalkyl" refers to a monovalent group having one or more saturated rings, wherein all ring members are carbon.

As used herein, the term "aryl" alone or in combination refers to an aromatic hydrocarbon containing at least one ring and having the indicated number of carbon atoms. The term "aryl" may be interpreted to include groups having an aromatic ring fused to at least one cycloalkyl ring.

As used herein, the term "formyl" refers to a group having the formula-C (=o) H.

As used herein, the term "substituted" is meant to include at least one substituent, such as halogen (F, cl, br, I), hydroxy, amino, mercapto, carboxyl, carboxylate Esters (including acrylates, methacrylates and lactones), ketones, anhydrides, amides, nitriles, sulfides, disulfides, sulfones, sulfoxides, sulfonamides, nitro groups, C _1-20 Alkyl, C _1-20 Cycloalkyl (including adamantyl), C _1-20 Alkenyl (including norbornenyl), C _1-20 Alkoxy, C _2-20 Alkenyloxy (including vinyl ethers), C _6-30 Aryl, C _6-30 Aryloxy, C _7-30 Alkylaryl or C _7-30 Alkyl aryloxy.

When a group containing the specified number of carbon atoms is substituted with any of the groups listed in the preceding paragraph, the number of carbon atoms in the resulting "substituted" group is defined as the sum of the carbon atoms contained in the original (unsubstituted) group and the carbon atoms, if any, contained in the substituent. For example, when the term "substituted C ₁ -C ₂₀ Alkyl "means C ₆ -C ₃₀ Aryl substituted C ₁ -C ₂₀ In the case of alkyl groups, the total number of carbon atoms in the resulting aryl-substituted alkyl groups is C ₇ -C ₅₀ 。

As used herein, the term "mixture" refers to any combination of ingredients that make up a blend or mixture, regardless of physical form.

As described above, known polyarylene SOC formulations may have high thermal stability, high etch resistance, and good planarization characteristics. However, the adhesion of conventional polyarylene substrates to inorganic substrates may be limited, which may cause problems in subsequent processing steps. For example, during wet chemical etching, conventional polyarylene formulations delaminate from the substrate, resulting in an unacceptable loss of pattern fidelity and substrate damage.

The inventors of the present invention have found that the addition of polar polymers comprising functional groups with strong substrate interactions significantly improves the adhesion of polyarylene materials to substrates. Described herein are novel resist underlayer compositions comprising a poly (arylene ether) and a polar additive polymer.

In one embodiment, the resist underlayer composition may comprise:

the poly (arylene ether) is used as a catalyst,

an additive polymer different from the poly (arylene ether), and

and (3) a solvent.

The resist underlayer composition comprises a poly (arylene ether). As used herein, the term "polyarylene ether" refers to compounds having substituted or unsubstituted arylene oxy (-Ar-O-) structural units, wherein "Ar" is a divalent group derived from an aromatic hydrocarbon. "poly (arylene ether)" may refer to poly (arylene ether), poly (arylene ether ketone), poly (arylene ether sulfone), or poly (etherimide), poly (etherimidazole), and poly (etherbenzoxazole). In all these compounds, at least one substituted or unsubstituted structural unit (-Ar-O-). According to one embodiment, the poly (arylene ether) may comprise polymerized units of one or more first monomers having two or more cyclopentadienone moieties and one or more second monomers having an aromatic moiety and two or more alkynyl moieties. Some poly (arylene ether) s are commercially available. For example, it is available under the trade name SiLK from the dow chemical company (The Dow Chemical Company) ^TM Solution product of poly (arylene ether) of G. The polyarylene ethers may be prepared by reacting certain dicyclopentadiene ketone monomers with certain polyethylenyl-substituted aromatic compounds in an amount of 1:<1 or 1:>1, and may have an M of about 3,000 to 5,000 daltons (Da) _w And a PDI of about 1.3. In one embodiment, the dicyclopentadiene ketone monomer and the polyethylenyl substituted aromatic compound can be in a molar ratio of 1:1.25.

To increase polymer solubility, one or more of the first monomers and/or one or more of the second monomers may be substituted with polar moieties, such as those solubility enhancing moieties disclosed in U.S. published patent application No. 2017/0009006 (which is incorporated herein by reference in its entirety). Suitable solubility enhancing polar moieties include, but are not limited to: hydroxyl, carboxyl, mercapto, nitro, amino, amido, sulfonyl, sulfonamide moiety, ester moiety, quaternary amine moiety, and the like. An exemplary first monomer having one or more solubility enhancing polar moieties is disclosed in U.S. patent application Ser. No. 15/790606, filed on 10/27 in 2017 (which is incorporated herein by reference in its entirety). An exemplary second monomer having one or more solubility enhancing polar moieties is disclosed in U.S. published patent application No. 2017/0009006 (which is incorporated herein by reference in its entirety). Preferably, the one or more first monomers are free of solubility enhancing polar moieties. Preferably, the one or more second monomers are free of solubility enhancing polar moieties. More preferably, one or more of the first monomer and the second monomer is free of solubility enhancing polar moieties.

Any compound containing two or more cyclopentadienone moieties capable of undergoing a diels-alder reaction may be suitably used as the first monomer for preparing the poly (arylene ether) of the present invention. Alternatively, a mixture of two or more different first monomers may be used as the first monomer, each first monomer having two or more cyclopentadienone moieties. Preferably, only one first monomer is used. Preferably, the first monomer has two to four cyclopentadienone moieties, and more preferably has two cyclopentadienone moieties (also referred to herein as dicyclopentadiene ketone). Suitable first monomers having two or more cyclopentadienone moieties are well known in the art, for example in U.S. patent No. 5,965,679;6,288,188; and 6,646,081; and those described in International patent publications WO 97/10193, WO 2004/073824 and WO 2005/030848, which are incorporated herein by reference in their entirety.

The first monomer preferably has a structure represented by formula (1)

Wherein each R is ¹⁰ Independently selected from H, C _1-6 -alkyl and optionally substituted C _5-20 -an aryl group; and Ar is ³ Is an aryl moiety having from 5 to 60 carbons. In formula (1), "substituted C _5-20 Aryl "means C whose one or more hydrogens are replaced by one or more of the following _5-20 -aryl: halogen, C _1-10 -alkyl, C _5-10 -aryl, -C≡C-C _5-10 -aryl or withHeteroatom-containing groups of 0 to 20 carbon atoms and one or more heteroatoms selected from O, S and N, preferably halogen, C _1-10 -alkyl, C _6-10 -aryl and-C≡C-C _6-10 Aryl, and more preferably phenyl and-C.ident.C-phenyl. As used herein, "substituted phenyl" refers to a phenyl moiety substituted with one or more of the following: halogen, C _1-10 -alkyl, C _5-10 -aryl, -C≡C-C _5-10 -aryl or a heteroatom-containing group having 0-20 carbon atoms and one or more heteroatoms selected from O, S and N, and preferably one or more of the following: halogen, C _1-10 -alkyl, C _6-10 -aryl and-C≡C-C _6-10 Aryl, and more preferably from phenyl and-c≡c-phenyl. Exemplary heteroatom-containing groups having from 0 to 20 carbon atoms and one or more heteroatoms selected from O, S and N include, but are not limited to, hydroxy, carboxy, amino, C _1-20 -amido, C _1-10 -alkoxy, C _1-20 -hydroxyalkyl, C _1-30 Hydroxy (alkyleneoxy) groups, and the like. Preferably, each R ¹⁰ Independently selected from C _1-6 -alkyl, phenyl and substituted phenyl, more preferably, each R ¹⁰ Is phenyl or substituted phenyl, and even more preferably phenyl or-C ₆ H ₄ -c≡c-phenyl. A variety of aromatic moieties are suitable for use as Ar ³ Such as those disclosed in U.S. patent No. 5,965,679 (which application is incorporated herein by reference in its entirety). Preferably Ar ³ Having 5 to 40 carbons, and more preferably 6 or 30 carbons. Preferred uses for Ar ³ Aryl moieties of (C) include pyridyl, phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, coroneyl, tetracenyl, pentacenyl tetraphenyl, benzotetraphenyl, triphenylene, perylene, biphenyl, binaphthyl, diphenyl ether, dinaphthyl ether, and those having a structure represented by formula (2)

Wherein x is an integer selected from 1, 2 or 3; y is an integer selected from 0, 1 or 2; each Ar is provided with ⁴ Independently selected from

Or->

Each R ¹¹ Independently selected from halogen, C _1-6 -alkyl, C _1-6 -haloalkyl, C _1-6 -alkoxy, C _1-6 -haloalkoxy, phenyl and phenoxy; c3 is an integer from 0 to 4; d3 and e are each integers from 0 to 3; each Z is independently selected from a single covalent chemical bond, O, S, NR ¹² 、PR ¹² 、P(＝O)R ¹² 、C(＝O)、C(R ¹³ )(R ¹⁴ ) And Si (R) ¹³ )(R ¹⁴ )；R ¹² 、R ¹³ And R is ¹⁴ Independently selected from H, C _1-4 -alkyl, C _1-4 -haloalkyl and phenyl. Preferably, x is 1 or 2, and more preferably 1. Preferably, y is 0 or 1, and more preferably 1. Preferably, each R ¹¹ Independently selected from halogen, C _1-4 Alkyl, C _1-4 Haloalkyl, C _1-4 -alkoxy, C _1-4 -haloalkoxy and phenyl, and more preferably selected from fluorine, C _1-4 -alkyl, C _1-4 -fluoroalkyl, C _1-4 -alkoxy, C _1-4 -fluoroalkoxy and phenyl. Preferably, c3 is 0 to 3, more preferably 0 to 2, and still more preferably 0 or 1. Preferably, d3 and e are each independently 0 to 2, and more preferably 0 or 1. In formula (4), it is preferable that d3+e=0 to 4, and more preferably 0 to 2. Each Z is preferably independently selected from O, S, NR ¹² 、C(＝O)、C(R ¹³ )(R ¹⁴ ) And Si (R) ¹³ )(R ¹⁴ ) More preferably selected from O, S, C (=o), and C (R ¹³ )(R ¹⁴ ) And still more preferably selected from O, C (=o), and C (R ¹³ )(R ¹⁴ )。R ¹² 、R ¹³ And R is ¹⁴ Each independently selected from H, C _1-4 -alkyl, C _1-4 -fluoroalkyl and phenyl; and more preferably from H, C _1-4 -alkyl, C _1-2 -fluoroalkyl and phenyl. Preferably Ar ³ Has at least one ether linkage, more preferably at least one aromatic ether linkage, and even more preferably one aromatic ether linkage. Preferably Ar ³ Has the structure of formula (2). Preferably, each Ar ⁴ Has the formula (3), and more preferably, each Ar ⁴ Has the formula 3 and Z is O.

Any compound having an aryl moiety capable of undergoing a diels-alder reaction and two or more alkynyl groups may be suitably used as the second monomer for preparing the present polymer. Preferably, the second monomer has an aryl moiety substituted with two or more alkynyl groups. Preferably, a compound having an aryl moiety substituted with two to four, and more preferably two or three alkynyl moieties is used as the second monomer. Preferably, the second monomer has an aryl moiety substituted with two or three alkynyl groups capable of undergoing a diels-alder reaction. Suitable second monomers are those of the formula (5)

Wherein Ar is ¹ And Ar is a group ² Each independently is C _5-30 -an aryl moiety; each R is independently selected from H and optionally substituted C _5-30 -an aryl group; each R ¹ Independently selected from-OH, -CO ₂ H、C _1-10 -alkyl, C _1-10 -haloalkyl, C _1-10 -hydroxyalkyl, C _2-10 -carboxyalkyl, C _1-10 -alkoxy, CN and halogen; each Y is independently a single covalent chemical bond or is selected from-O-, -S (=O) ₂ -、-C(＝O)-、-(C(R ⁹ ) ₂ ) _z -、C _6-30 -aryl and- (C (R) ⁹ ) ₂ ) _z1 -(C _6-30 -aryl) - (C (R) ⁹ ) ₂ ) _z2 -a divalent linking group; each R ⁹ Independently selected from H, hydroxy, halogen, C _1-10 -alkyl, C _1-10 -haloalkyl and C _6-30 -an aryl group; a1 =0 to 4; each a2=0 to 4; b1 =1 to 4; each b2=0 to 2; a1+Each a2=0 to 6; b1+ each b2=2 to 6; d=0 to 2; z=1 to 10; z1=0 to 10; z2=0 to 10; and z1+z2=1 to 10. Each R is preferably independently selected from H and C _6-20 Aryl, more preferably selected from H and C _6-10 Aryl groups, and even more preferably selected from H and phenyl. Preferably, each R ¹ Independently selected from C _1-10 -alkyl, C _1-10 -haloalkyl, C _1-10 -hydroxyalkyl, C _1-10 -alkoxy and halogen, and more preferably selected from C _1-10 -alkyl, C _1-10 -haloalkyl and halogen. Preferably, each Y is independently a single covalent chemical bond or is selected from-O-, -S (=o) ₂ -、-C(＝O)-、-(C(R ⁹ ) ₂ ) _z -, and C _6-30 Divalent linking groups of aryl groups, and more preferably are single covalent chemical bonds, -O-, -S (=o) ₂ -, -C (=O) -, and- (C (R) ⁹ ) ₂ ) _z -. Each R ⁹ Preferably independently H, halogen, C _1-10 -alkyl, C _1-10 -haloalkyl, or C _6-30 Aryl, and more preferably fluoro, C _1-6 -alkyl, C _1-6 Fluoroalkyl, or C _6-20 -aryl. Preferably a1=0 to 3, and more preferably 0 to 2. Preferably, each a2=0 to 2. Preferably, a1+a2=0 to 4, more preferably 0 to 3, and still more preferably 0 to 2. Preferably, b1=1 to 3, and more preferably 1 or 2. Preferably, each b2=0 to 2; and more preferably 0 or 1. Preferably, b1+ each b2=2 to 4, and more preferably 2 or 3. Preferably, d=0 or 1, and more preferably 0. Preferably, z=1 to 6, more preferably 1 to 3, and even more preferably, z=1. Preferably, z1 and z2 are each 0 to 5. Preferably, z1+z2=1 to 6, and more preferably 2 or 6.

Ar ¹ And Ar is a group ² Suitable aryl moieties of (a) include, but are not limited to, pyridyl, phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, coronenyl, tetracenyl, pentacenyl, tetraphenyl, benzotetraphenyl, triphenylenyl, perylenyl, biphenyl, binaphthyl, diphenyl ether, dinaphthyl ether, carbazole, and fluorenyl. Preferably Ar in formula (5) ¹ And each Ar ² Independently C _6-20 An aryl moiety. Ar (Ar) ¹ And each Ar ² Preferred aryl moieties of (a) are phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, naphtyl, pentacenyl, tetraphenyl, triphenylenyl and perylene groups.

Preferred second monomers of formula (5) are those of formulas (6) and (7):

wherein Ar is ¹ 、R、R ¹ A1 and b1 are as defined above for formula (5); a3 is 0 or 2; a4 is 0 to 2; n1 and n2 are each independently 0 to 4; and Y ¹ Is a single covalent chemical bond O, S, S (=o) ₂ 、C(＝O)、C(CH ₃ ) ₂ 、CF ₂ And C (CF) ₃ ) ₂ . Those skilled in the art will appreciate that brackets in formula (7) ("[ for a ]]") refers to the number of aromatic rings fused to a benzene ring. Thus, when n1 (or n 2) =0, the aromatic moiety is phenyl; when n1 (or n 2) =1, the aromatic moiety is naphthyl; when n1 (or n 2) =2, the aromatic moiety may be anthracenyl or phenanthrenyl; when n1 (or n 2) =3, the aromatic moiety may be a tetracenyl, tetraphenyl, triphenylenyl or pyrenyl group; and when n1 (or n 2) =4, the aromatic moiety may be perylene or benzotetraphenyl. In formula (6), a1 is preferably 0 to 2, and more preferably 0. Preferably, b1 in formula (6) is 1 or 2.R is preferably H or phenyl. Each R in each of formulas (6) and (7) ¹ Preferably independently selected from C _1-10 -alkyl, C _1-10 -haloalkyl, C _1-10 -hydroxyalkyl, C _1-10 -alkoxy and halogen, and more preferably selected from C _1-10 -alkyl, C _1-10 -haloalkyl and halogen. Ar in formula (6) ¹ Preferred are phenyl, naphthyl, anthracenyl, pyrenyl and perylenyl groups, more preferred are phenyl, naphthyl and pyrenyl groups, and even more preferred are phenyl groups. In formula (7), it is preferred that n1 and n2 are independently selected from 0, 1, 3 and 4, more preferably from 0, 1 and 3, and even more preferably from 1 and 3. It is further preferred that n1=n2. In formula (7), Y ¹ Preferably a single co-polymerValence bond, O, S (=o) ₂ 、C(＝O)、C(CH ₃ ) ₂ 、CF ₂ Or C (CF) ₃ ) ₂ And more preferably a single covalent chemical bond.

Particularly preferred monomers of formula (6) are monomers of formulae (8) to (12):

wherein R and R ¹ As described above for formula (6); a5 =0 to 2; a6, a7, a8 and a9 are each independently 0 to 4; b5 and b6 are each selected from 1 to 3; and b7, b8 and b9 are each selected from 2 to 4. Preferably, a5=0 or 1, and more preferably 0. Preferably, a6 is 0 to 3, more preferably 0 to 2, and even more preferably 0. Preferably, a7 and a9 are each independently 0 to 3, and more preferably 0 to 2. Preferably, b5 and b6 are each selected from 1 and 2. Preferably, b7, b8 and b9 are each 2 or 3. Compound (8) is more particularly preferred. Preferably, in the compound (8), each R is independently H or phenyl, and more preferably each R is H or phenyl. More preferably, each R in formulas (8) to (12) ¹ Independently selected from C _1-10 -alkyl, C _1-10 -haloalkyl, C _1-10 -hydroxyalkyl, C _1-10 -alkoxy and halogen, and more preferably selected from C _1-10 -alkyl, C _1-10 -haloalkyl and halogen.

In the monomers having formulas (5) to (12), any two alkynyl moieties may have an ortho, meta or para relationship with each other, and preferably have an meta or para relationship with each other. Preferably, the alkynyl moieties in the monomers of formulae (5) to (12) do not have an ortho relationship with each other. Suitable monomers having formulae (5) to (12) are generally commercially available or can be readily prepared by methods known in the art.

Exemplary second monomers include, but are not limited to: 1, 3-diacetylene benzene; 1, 4-diacetylene benzene; 4,4 '-diacetylene-1, 1' -biphenyl; 3, 5-diacetylene-1, 1' -biphenyl; 1,3, 5-tri-ethynyl benzene; 1, 3-diacetylene-5- (phenylethynyl) benzene; 1, 3-bis (phenylethynyl) benzene; 1, 4-bis (phenylethynyl) -benzene; 1,3, 5-tris (phenylethynyl) benzene; 4,4 '-bis (phenylethynyl) -1,1' -biphenyl; 4,4' -diacetylene-diphenyl ether; and mixtures thereof. More preferably, the monomer having formula (5) is selected from: 1, 3-diacetylene benzene; 1, 4-diacetylene benzene; 1,3, 5-tri-ethynyl benzene; 1,3, 5-tris (phenylethynyl) benzene; 4,4 '-diacetylene-1, 1' -biphenyl; 1, 3-bis (phenylethynyl) -benzene; 1, 4-bis (phenylethynyl) benzene; 4,4 '-bis (phenylethynyl) -1,1' -biphenyl; and mixtures thereof. Even more preferably, the second monomer is selected from: 1, 3-diacetylene benzene; 1, 4-diacetylene benzene; 4,4 '-diacetylene-1, 1' -biphenyl; 1,3, 5-tri-ethynyl benzene; 1,3, 5-tris (phenylethynyl) benzene; and mixtures thereof.

According to one embodiment, the poly (arylene ether) may be formed from one or more first monomers having formula (1), or a mixture of two or more different first monomers having formula (1). The poly (arylene ether) of the present invention may be formed from one second monomer having formula (5), or a mixture of two or more different second monomers having formula (5). Monomers having formula (6) are preferred second monomers. Preferably, the poly (arylene ether) of the present invention is formed from polymerized units of one or more first monomers having formula (1) and one or more second monomers having formula (6). In an alternative preferred embodiment, the poly (arylene ether) of the present invention is formed from polymerized units of one or more first monomers having the formula (1) and one or more second monomers having the formula (7), or in yet another alternative embodiment, from polymerized units of one or more first monomers having the formula (1), one or more second monomers having the formula (6), and one or more second monomers having the formula (7). Mixtures comprising as polymerized units one or more first monomers of formula (1) and one or more second monomers of formula (5) may be suitably used.

The poly (arylene ether) of the present invention may optionally further comprise one or more capping monomers as polymerized units. Preferably, only one end-capping monomer is used. As used herein, the term "capping monomer" refers to a monomer having a single dienophile moiety, wherein such dienophile moiety is used to cap one or more ends of the present polymer such that the capped ends of the polymer are not capable of further diels-alder polymerization. Preferably, the dienophile moiety is an alkynyl moiety. Optionally, the capping monomer may include one or more solubility enhancing polar moieties, such as those disclosed in U.S. published patent application number 2016/0060393 (which is incorporated herein by reference in its entirety). Preferably, the end-capping monomer does not contain a solubility enhancing polar moiety. Preferred end-capping monomers are those of formula (13)

Wherein R is ²⁰ And R is ²¹ Each independently selected from H, C _5-20 -aryl and C _1-20 -an alkyl group. Preferably, R ²⁰ And R is ²¹ Each independently selected from H, C _6-20 -aryl and C _1-20 -an alkyl group. More preferably, R ²⁰ Is C _5-20 Aryl, and even more preferably C _6-20 -aryl. R is R ²¹ Preferably H or C _1-20 -an alkyl group. When used, such end-capping monomers are typically used in a molar ratio of the first monomer to the end-capping monomer of from 1:0.01 to 1:1.2.

Exemplary endcapping monomers include, but are not limited to: styrene; alpha-methylstyrene; beta-methylstyrene; norbornadiene; ethynyl pyridine; ethynyl benzene; ethynyl naphthalene; ethynyl pyrene; ethynyl anthracene; ethynylphenanthrene; diphenylacetylene; 4-ethynyl-1, 1' -biphenyl; 1-propynylbenzene; propiolic acid; 1, 4-butynediol; acetylene dicarboxylic acid; ethynyl phenol; 1, 3-diacetylene benzene; propargyl aryl esters; ethynyl phthalic anhydride; the method comprises the steps of carrying out a first treatment on the surface of the Diacetylenic acid; and 2,4, 6-tris (phenylethynyl) anisole. Preferred end-capping monomers are: ethynylbenzene, norbornadiene; ethynylnaphthalene, ethynylpyrene, ethynylanthracene, ethynylphenanthrene, and 4-ethynyl-1, 1' -biphenyl.

The following are examples of poly (arylene ether):

according to one embodiment, the poly (arylene ether) is prepared by reacting one or more first monomers with one or more second monomers and any optional capping monomers in a suitable organic solvent. The molar ratio of total first monomer to total second monomer is 1:>1. preferably 1:1.01 to 1:1.5, more preferably 1:1.05 to 1:1.4, and still more preferably 1:1.2 to 1:1.3. The total moles of the second monomer used is greater than the total moles of the first monomer used. Suitable organic solvents which can be used for preparing the polymers are (C ₂ -C ₆ ) Benzyl esters of alkane carboxylic acids, (C) ₂ -C ₆ ) Dibenzyl esters of alkanedicarboxylic acids, (C) ₂ -C ₆ ) Tetrahydrofurfuryl esters of alkane carboxylic acids, (C) ₂ -C ₆ ) Ditetrahydrofurfuryl esters of alkanedicarboxylic acids, (C) ₂ -C ₆ ) Phenethyl esters of alkane carboxylic acids, (C) ₂ -C ₆ ) Diphenylethyl esters of alkane dicarboxylic acids, aromatic ethers, N-methylpyrrolidone (NMP) and gamma-butyrolactone (GBL). Preferred aromatic ethers are diphenyl ether, dibenzyl ether, (C) ₁ -C ₆ ) Alkoxy-substituted benzene, benzyl (C) ₁ -C ₆ ) Alkyl ethers, NMP and GBL, and more preferably (C ₁ -C ₄ ) Alkoxy-substituted benzene, benzyl (C) ₁ -C ₄ ) Alkyl ethers, NMP and GBL. Preferred organic solvents are (C) ₂ -C ₄ ) Benzyl esters of alkane carboxylic acids, (C) ₂ -C ₄ ) Dibenzyl esters of alkanedicarboxylic acids, (C) ₂ -C ₄ ) Tetrahydrofurfuryl esters of alkane carboxylic acids, (C) ₂ -C ₄ ) Ditetrahydrofurfuryl esters of alkanedicarboxylic acids, (C) ₂ -C ₄ ) Phenethyl esters of alkane carboxylic acids, (C) ₂ -C ₄ ) Diphenylethyl esters of alkanedicarboxylic acids, (C) ₁ -C ₆ ) Alkoxy-substituted benzene, benzyl (C) ₁ -C ₆ ) Alkyl ethers, NMP and GBL, more preferably (C ₂ -C ₆ ) Phenyl esters of alkane carboxylic acids, (C) ₂ -C ₆ ) Tetrahydrofurfuryl esters of alkane carboxylic acids, (C) ₂ -C ₆ ) Phenethyl esters of alkane carboxylic acids, (C) ₁ -C ₄ ) Alkoxy-substituted benzene, benzyl (C) ₁ -C ₄ ) Alkyl ethers, dibenzyl ethers, NMP and GBL, and still more preferably (C) ₂ -C ₆ ) Benzyl esters of alkane carboxylic acids, (C) ₂ -C ₆ ) Tetrahydrofurfuryl esters of alkane carboxylic acids, (C) ₁ -C ₄ ) Alkoxy-substituted benzene, benzyl (C) ₁ -C ₄ ) Alkyl ethers, NMP and GBL. Exemplary organic solvents include, but are not limited to, benzyl acetate, benzyl propionate, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate, tetrahydrofurfuryl butyrate, anisole, methylanisole, dimethyl anisole, dimethoxybenzene, ethylanisole, ethoxybenzene, benzyl methyl ether, and benzyl ethyl ether, and preferably benzyl acetate, benzyl propionate, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate, tetrahydrofurfuryl butyrate, anisole, methylanisole, dimethyl anisole, dimethoxybenzene, ethylanisole, and ethoxybenzene.

According to one embodiment, the poly (arylene ether) may be prepared by combining, in any order, the first monomer, the second monomer, any optional capping monomer, and the organic solvent, each as described above, in a container and heating the mixture. Preferably, the present polymer is prepared by combining the first monomer, the second monomer, and the organic solvent, each as described above, in any order in a container and heating the mixture. Alternatively, the first monomer may be first combined with the organic solvent in a vessel, and then the second monomer added to the mixture. In an alternative embodiment, the first monomer and organic solvent mixture is first heated to the desired reaction temperature, and then the second monomer is added. The second monomer may be added at one time or, alternatively, may be added over a period of time, for example 0.25 to 6 hours, to reduce exothermic formation. The first monomer and organic solvent mixture may be first heated to the desired reaction temperature and then the second monomer added. The present capped poly (arylene ether) may be prepared by the following method: the poly (arylene ether) is first prepared by combining the first monomer, the second monomer, and the organic solvent in any order in a vessel and heating the mixture, followed by isolation of the poly (arylene ether), and then combining the isolated poly (arylene ether) with the capping monomer in the organic solvent and heating the mixture for a period of time. Alternatively, the present capped poly (arylene ether) may be prepared by the following method: by combining the first monomer, the second monomer, and the organic solvent in any order in a vessel and heating the mixture for a period of time to provide the desired poly (arylene ether), then adding the capping monomer to the poly (arylene ether) -containing reaction mixture and heating the reaction mixture for a period of time. The reaction mixture is heated at a temperature of 100 ℃ to 250 ℃. Preferably, the mixture is heated to a temperature of 150 ℃ to 225 ℃, and more preferably to a temperature of 175 ℃ to 215 ℃. Typically, the reaction is allowed to proceed for 2 to 20 hours, preferably 2 to 8 hours, and more preferably 2 to 6 hours, with the reaction time being shorter to produce a relatively low molecular weight poly (arylene ether). The reaction may be carried out under an oxygen-containing atmosphere, but an inert atmosphere such as nitrogen is preferred. After the reaction, the resulting poly (arylene ether) may be isolated from the reaction mixture or used as is to coat a substrate.

Without intending to be bound by theory, it is believed that the poly (arylene ether) of the present invention is formed by the diels-alder reaction of the cyclopentadienone portion of the first monomer with the alkynyl portion of the second monomer upon heating. During this diels-alder reaction, carbonyl bridged species are formed. Those skilled in the art will appreciate that such carbonyl-bridged species may be present in the polymer. Upon further heating, the carbonyl bridging species will be substantially completely converted to an aromatic ring system. Because of the molar ratio of the monomers used, the present polymers contain arylene rings in the poly (arylene ether) backbone, as shown in the following reaction scheme, wherein A is a first monomer, B is a second monomer, and Ph is phenyl.

According to one embodiment, the poly (arylene ether) has a weight average molecular weight (M) of 1,000 to 6,000da, preferably 1,000 to 5,000da, more preferably 2,000 to 5,000da, still more preferably 2,500 to 5,000da, even more preferably 2,700 to 5,000da, and still more preferably 3,000 to 5,000da _w ). According to one embodiment, the poly (arylene ether) typically has a number average molecular weight (M) of 1,500 to 3,000Da _n ). The poly (arylene ether) of the present invention has a polydispersity index (PDI) of 1 to 2, preferably 1 to 1.99, more preferably 1 to 1.9, still more preferably 1 to 1.8, and still more preferably 1.25 to 1.75. Pdi=m _w /M _n . M of the present polymers _n And M _w Determined by conventional techniques of Gel Permeation Chromatography (GPC) using uninhibited Tetrahydrofuran (THF) as the eluting solvent at 1mL/min and a differential refractive detector, relative to polystyrene standards. The poly (arylene ether) of the present invention has a Degree of Polymerization (DP) of 2 to 5, preferably 2 to 4.5, more preferably 2 to 3.75, and still more preferably 2 to 3.5. DP was calculated by dividing the molecular weight of the polymer by the molecular weight of each repeat unit (excluding any end-capping monomer present). The poly (arylene ether) of the present invention has a molar ratio of total first monomer to total second monomer of 1 to ≡1, preferably a ratio of 1:1.01 to 1:1.5, more preferably a ratio of 1:1.05 to 1:1.4, still more preferably a ratio of 1:1.1 to 1:1.3, still more preferably a ratio of 1:1.15 to 1:1.3, and even more preferably a ratio of 1:1.2 to 1:1.3. The ratio of the total moles of the first monomer to the total moles of the second monomer is typically calculated as the feed ratio of the monomers, but can also be determined using conventional matrix assisted laser desorption/ionization (MALDI) time of flight (TOF) mass spectrometry, in which silver trifluoroacetate is added to the sample to promote ionization. A suitable instrument is a Bruker Daltonics Ultraflex MALDI-TOF mass spectrometer equipped with a nitrogen laser (wavelength 337 nm). According to one embodiment, a particularly preferred polymer is M having a value of 3,000 to 5,000 _w PDI of 1.25 to 1.75, and those of 1:1.2 to 1:1.3, the ratio of the total moles of the first monomer to the total moles of the second monomer.

The composition may further comprise an additive polymer other than a poly (arylene ether). In order to increase the adhesion to the substrate,the additive polymer comprises at least one protected or free polar functional group. As used herein, the term "polar functional group" refers to a functional group that includes at least one heteroatom. The additive polymer may comprise aromatic or heteroaromatic groups having at least one protected or free functional group selected from hydroxyl, mercapto and amino groups. As used herein, the term "free functional group" refers to an unprotected functional group. Thus, the term "free hydroxyl" refers to "-OH", the term "free thiol" refers to "-SH", and the term "free amino" refers to "-NH ₂ ". As used herein, the term "protected functional group" refers to a functional group that is terminated by a protecting group that reduces or eliminates the reactivity of the free functional group. The protecting group may optionally include-O-, -NR- (wherein R is hydrogen or C) _1-10 Alkyl), -C (=o) -or a combination thereof.

The protecting group may include formyl, substituted or unsubstituted straight or branched C _1-10 Alkyl, substituted or unsubstituted C _3-10 Cycloalkyl, substituted or unsubstituted C _2-10 Alkenyl, substituted or unsubstituted C _2-10 Alkynyl groups or combinations thereof. On any part of the protecting group, the protecting group may include-O-, -NR- (wherein R is hydrogen or C) _1-10 Alkyl), -C (=o) -or a combination thereof.

In one embodiment, the functional group may be a hydroxyl group, which may be protected as an alkyl ether to form the structure OR, where R is C _1-10 Linear or branched alkyl. Preferred alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.

In another embodiment, the protecting group may be formyl [ -C (=O) H]Or C _2-10 Alkanoyl [ -C (=O) R, wherein R is C _1-10 Straight or branched alkyl]. Preferably C _2-10 Alkanoyl is acetyl [ -C (=O) CH ₃ ]Or propionyl [ -C (=O) CH ₂ CH ₃ ]. The functional groups may be protected by acetyl or propionyl groups to form the ester-OC (=o) CH, respectively ₃ or-OC (=O) CH ₂ CH ₃ Hydroxyl groups of (c).

In another embodiment, the hydroxyl groups may be protected as carbonates to form knotsconstruct-OC (=o) OR, wherein R is C _1-10 Linear or branched alkyl. Preferred carbonate groups include-OC (=o) OCH ₃ 、-OC(＝O)OCH ₂ CH ₃ 、-OC(＝O)OCH ₂ CH ₂ CH ₃ 、-OC(＝O)OCH(CH ₃ ) ₂ or-OC (=O) OC (CH) ₃ ) ₃ 。

In another embodiment, the hydroxyl group may be protected as a carbamate to form the structure-OC (=o) NRR ', where R and R' are each independently C _1-10 Linear or branched alkyl. Preferred urethane groups include-OC (=o) NHCH ₃ 、-OC(＝O)NHCH ₂ CH ₃ 、-OC(＝O)NHCH ₂ CH ₂ CH ₃ 、-OC(＝O)NHCH(CH ₃ ) ₂ 、-OC(＝O)NHC(CH ₃ ) ₃ or-OC (=O) NH (CH ₃ ) ₂ 。

In one embodiment, the protecting group may be a polymerizable group comprising a substituted or unsubstituted C _2-10 Alkenyl, substituted or unsubstituted C _2-10 Alkynyl groups or combinations thereof.

The additive polymer may include structural units represented by formula (I):

in formula (I), ar may be C _6-40 Aromatic organic radicals or C _3-40 Heteroaromatic organic groups, each of which may be a single aromatic or heteroaromatic group or a fused aromatic or heteroaromatic group. For example, ar may be C _6-30 Aromatic organic radicals or C _3-30 Heteroaromatic organic groups. For example, ar may be C _6-20 Aromatic organic radicals or C _3-20 Heteroaromatic organic groups.

X and Y are substituents directly attached to Ar. X may be hydrogen, substituted or unsubstituted C _1-10 Alkyl, substituted or unsubstituted C _2-10 Alkenyl, substituted or unsubstituted C _2-10 Alkynyl, substituted or unsubstituted C _3-10 Cycloalkyl, or substituted or unsubstituted C _6-20 Aryl groups.Y may be OR ₄ 、SR ₅ 、NR ₆ R ₇ Or CR (CR) ₈ R ₉ OR ₄ Wherein R is ₄ To R ₉ Each independently is hydrogen, formyl, substituted or unsubstituted C _1-5 Alkyl, substituted or unsubstituted C _2-5 Alkenyl, substituted or unsubstituted C _2-5 Alkynyl, or substituted or unsubstituted C _3-8 Cycloalkyl groups, each of which may optionally include-O-, -NR- (wherein R is hydrogen or C) _1-10 Alkyl), -C (=o) -or a combination thereof. R is R ₆ And R is ₇ May optionally be linked to form a ring, and R ₈ And R is ₉ May optionally be linked to form a ring. L is a single bond or a divalent linking group. The linking group may be C _1-30 A linking group, an ether group, a carbonyl group, an ester group, a carbonate group, an amine group, an amide group, a urea group, a sulfate group, a sulfone group, a sulfoxide group, an N-oxide group, a sulfonate group, a sulfonamide group, or a combination of at least two of the foregoing. C (C) _1-30 The linking group can include heteroatoms comprising O, S, N, F or a combination of at least one of the foregoing heteroatoms. In one embodiment, the linking group may be-C (R ¹⁰ ) ₂ -、-N(R ¹¹ )-、-O-、-S-、-S(＝O) ₂ -, - (c=o) -or combinations thereof, wherein each R ³⁰ And R is ³¹ Independently hydrogen or C _1-6 An alkyl group. Preferably, X is hydrogen or substituted or unsubstituted C _1-5 Alkyl, Y is OR optionally including-O-, -C (=O) -OR a combination thereof ₄ And L is a single bond. The variables m and n are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, provided that the sum of m and n does not exceed the total number of atoms of Ar which may be substituted with X and Y. R is R ₁ To R ₃ May independently be hydrogen, substituted or unsubstituted C _1-10 Alkyl, substituted or unsubstituted C _2-10 Alkenyl, substituted or unsubstituted C _2-10 Alkynyl or substituted or unsubstituted C _3-10 Cycloalkyl groups. Preferably, R ₁ And R is ₂ Is hydrogen, and R ₃ Is hydrogen or C _1-5 An alkyl group.

The additive polymer may include a structural unit represented by formula (II):

in formula (II), ar may be C _6-40 Aromatic organic radicals or C _3-40 Heteroaromatic organic groups, each of which may be a single aromatic or heteroaromatic group or a fused aromatic or heteroaromatic group. For example, ar may be C _6-30 Aromatic organic radicals or C _3-30 Heteroaromatic organic groups. For example, ar may be C _6-20 Aromatic organic radicals or C _3-20 Heteroaromatic organic groups.

X and Y are substituents directly attached to Ar. X may be hydrogen, substituted or unsubstituted C _1-10 Alkyl, substituted or unsubstituted C _2-10 Alkenyl, substituted or unsubstituted C _2-10 Alkynyl, substituted or unsubstituted C _3-10 Cycloalkyl, or substituted or unsubstituted C _6-20 Aryl groups. Y may be OR ₄ 、SR ₅ 、NR ₆ R ₇ Or CR (CR) ₈ R ₉ OR ₄ Wherein R is ₄ To R ₉ Each independently is hydrogen, formyl, substituted or unsubstituted C _1-5 Alkyl, substituted or unsubstituted C _2-5 Alkenyl, substituted or unsubstituted C _2-5 Alkynyl, or substituted or unsubstituted C _3-8 Cycloalkyl groups, each of which may optionally include-O-, -NR- (wherein R is hydrogen or C) _1-10 Alkyl), -C (=o) -or a combination thereof. R is R ₆ And R is ₇ May optionally be linked to form a ring, and R ₈ And R is ₉ May optionally be linked to form a ring. Preferably, X is hydrogen or substituted or unsubstituted C _1-5 Alkyl, and Y is OR optionally including-O-, -C (=o) -OR a combination thereof ₄ . The variables m and n are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, provided that the sum of m and n does not exceed the total number of atoms of Ar which may be substituted with X and Y. R is R ₁ And R is ₂ May each independently be hydrogen, substituted or unsubstituted C _1-10 Alkyl, substituted or unsubstituted C _2-10 Alkenyl, substituted or unsubstitutedC of (2) _2-10 Alkynyl or substituted or unsubstituted C _3-10 Cycloalkyl groups. Preferably, R ₁ And R is ₂ Is hydrogen.

The additive polymer may include a structural unit represented by formula (III):

in formula (III), ar may be C _6-40 Aromatic organic radicals or C _3-40 Heteroaromatic organic groups, each of which may be a single aromatic or heteroaromatic group or a fused aromatic or heteroaromatic group. For example, ar may be C _6-30 Aromatic organic radicals or C _3-30 Heteroaromatic organic groups. For example, ar may be C _6-20 Aromatic organic radicals or C _3-20 Heteroaromatic organic groups.

In formula (III), X and Y are substituents directly attached to Ar. X may be hydrogen, substituted or unsubstituted C _1-10 Alkyl, substituted or unsubstituted C _2-10 Alkenyl, substituted or unsubstituted C _2-10 Alkynyl, substituted or unsubstituted C _3-10 Cycloalkyl, or substituted or unsubstituted C _6-20 Aryl groups. Y may be OR ₄ 、SR ₅ 、NR ₆ R ₇ Or CR (CR) ₈ R ₉ OR ₄ Wherein R is ₄ To R ₉ Each independently is hydrogen, formyl, substituted or unsubstituted C _1-5 Alkyl, substituted or unsubstituted C _2-5 Alkenyl, substituted or unsubstituted C _2-5 Alkynyl, or substituted or unsubstituted C _3-8 Cycloalkyl groups, each of which may optionally include-O-, -NR- (wherein R is hydrogen or C) _1-10 Alkyl), -C (=o) -or a combination thereof. R is R ₆ And R is ₇ May optionally be linked to form a ring, and R ₈ And R is ₉ May optionally be linked to form a ring. Preferably, X is hydrogen or substituted or unsubstituted C _1-5 Alkyl, and Y is OR optionally including-O-, -C (=o) -OR a combination thereof ₄ . The variables m and n are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,17. 18, 19 or 20, with the proviso that the sum of m and n does not exceed the total number of atoms of Ar which may be substituted with X and Y.

In some embodiments, the additive polymer may include each structural unit represented by formula (I), formula (II), and formula (III).

The amount of the structural unit represented by formula (I), the structural unit represented by formula (II), the structural unit represented by formula (III), or a combination thereof in the additive polymer may be 1mol% to 100mol% based on the total amount of all the repeating units in the additive polymer. For example, the amount of the structural unit represented by formula (I), the structural unit represented by formula (II), the structural unit represented by formula (III), or a combination thereof in the additive polymer may be 30mol% to 100mol%, 40mol% to 100mol%, 50mol% to 100mol%, 60mol% to 100mol%, 70mol% to 100mol%, 80mol% to 100mol%, or 90mol% to 100mol%, based on the total amount of all the repeating units in the additive polymer. In one embodiment, the amount of structural units represented by formula (I), structural units represented by formula (II), structural units represented by formula (III), or a combination thereof in the additive polymer may be 50mol% to 100mol% based on the total amount of all repeating units in the additive polymer.

Examples of additive polymers are listed below:

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according to one embodiment, the additive polymer has a weight average molecular weight (M) of from 1,000 to 1,000,000Da, preferably from 2,000 to 100,000Da, more preferably from 2,000 to 20,000Da _w ). According to one embodiment, the additive polymer typically has a number average fraction of 1,000-10,000DaSub-weight (M) _n ). The present additive polymers have a polydispersity index (PDI) of 1 to 3, preferably 1.5 to 2.5. Pdi=m _w /M _n . M of the present polymers _n And M _w Determined by conventional techniques of Gel Permeation Chromatography (GPC) using uninhibited Tetrahydrofuran (THF) as the eluting solvent at 1mL/min and a differential refractive detector, relative to polystyrene standards. The present additive polymer has a Degree of Polymerization (DP) of 10 to 10,000, preferably 20 to 1,000, more preferably 20 to 200. DP was calculated by dividing the molecular weight of the polymer by the molecular weight of each repeat unit (excluding any end-capping monomer present). According to one embodiment, a particularly preferred additive polymer is an M having a weight of 2,000 to 20,000 _w PDI of 1.5 to 2.5 and a ratio of 50% to 100% of the total moles of the first monomer to the total moles of all monomers.

The resist underlayer composition may further comprise a solvent. The solvent may be an organic solvent typically used in the electronics industry, such as Propylene Glycol Methyl Ether (PGME), propylene Glycol Methyl Ether Acetate (PGMEA), methyl 3-methoxypropionate (MMP), ethyl lactate, N-butyl acetate, anisole, N-methylpyrrolidone, γ -butyrolactone, ethoxybenzene, benzyl propionate, benzyl benzoate, propylene carbonate, xylene, mesitylene, cumene, limonene, and mixtures thereof. Mixtures of organic solvents may be used, such as mixtures comprising one or more of anisole, ethoxybenzene, PGME, PGMEA, GBL, MMP, n-butyl acetate, benzyl propionate and benzyl benzoate in combination with one or more other organic solvents, and more preferably mixtures comprising two or more of anisole, ethoxybenzene, PGME, PGMEA, GBL, MMP, n-butyl acetate, benzyl propionate, xylene, mesitylene, cumene, limonene and benzyl benzoate. When a solvent mixture is used, the ratio of solvents is generally not critical and may vary between 99:1 and 1:99 weight/weight (w/w) provided that the solvent mixture is capable of dissolving the components of the composition. Those skilled in the art will recognize that the concentration of the components in the organic solvent may be adjusted by removing a portion of the organic solvent or by adding more organic solvent, as may be desired.

The amount of additive polymer in the composition may be 0.1 to 30 wt.% (wt.%) based on the total weight of solids in the composition. For example, the amount of additive polymer in the composition may be 0.1 to 25 wt%, 0.1 to 20 wt%, 0.1 to 15 wt%, or 0.1 to 10 wt%, based on the total weight of solids in the composition. In another example, the amount of additive polymer in the composition can be 0.5 to 30 wt%, 0.5 to 25 wt%, 0.5 to 20 wt%, 0.5 to 15 wt%, or 0.5 to 10 wt%, based on the total weight of solids in the composition. In yet another example, the amount of additive polymer in the composition can be 1 to 30 wt%, 1 to 25 wt%, 1 to 20 wt%, 1 to 15 wt%, or 1 to 10 wt%, based on the total weight of solids in the composition. In yet another example, the amount of additive polymer in the composition can be 5 to 30 wt%, 5 to 25 wt%, 5 to 20 wt%, 5 to 15 wt%, or 5 to 10 wt%, based on the total weight of solids in the composition. Those skilled in the art will recognize that the amount of additive polymer in the composition can be adjusted to achieve the desired adhesion of the resist underlayer composition to the substrate.

The resist underlayer composition may contain optional additives such as curing agents, crosslinking agents, surface leveling agents, or any combination thereof. The choice of such optional additives and their amounts are well within the ability of those skilled in the art. The curing agent is typically present in an amount of 0 to 20 wt%, and preferably 0 to 3 wt%, based on total solids. The crosslinking agent is typically used in an amount of 0 to 30 wt%, and preferably 3 to 10 wt%, based on total solids. The surface leveling agent is typically used in an amount of 0 to 5 wt%, and preferably 0 to 1 wt%, based on the total solids. The choice of such optional additives and their amounts used are within the ability of the person skilled in the art.

A curing agent may optionally be used in the resist underlayer composition to aid in the curing of the deposited aromatic resin film. A curing agent is any component that causes the polymer to cure on the substrate surface. Preferred curing agents are acids, photoacid generators and thermal acid generators. Suitable acids include, but are not limited to: arylsulfonic acids such as p-toluenesulfonic acid; alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and propanesulfonic acid; perfluoroalkyl sulfonic acids such as trifluoromethanesulfonic acid; and (3) perfluoroaryl sulfonic acids. Photoacid generators are any compound that releases an acid upon exposure to light. A thermal acid generator is any compound that releases an acid upon exposure to heat. Thermal acid generators are well known in the art and are generally commercially available. See U.S. Pat. No. 6,261,743 (incorporated herein by reference in its entirety) for a discussion of the use of photoacid generators. Thermal acid generators are well known in the art and are generally commercially available, such as from King Industries, norwalk, conn. Exemplary thermal acid generators include, but are not limited to, amine-terminated strong acids, such as amine-terminated sulfonic acids, such as amine-terminated dodecylbenzene sulfonic acid. Those skilled in the art will also appreciate that certain photoacid generators are capable of releasing acid upon heating and may be used as thermal acid generators.

Examples of crosslinking agents may be amine-based crosslinking agents, such as melamine materials, including melamine resins such as those manufactured by Cymel 300, 301, 303, 350, 370, 380, 1116 and 1130, and sold under the trade names Cymel 300, 301, 303, 350, 370, 380, 1116 and 1130; glycolurils, including those available from cyanoversatas; and benzoguanamine and urea-based materials, including resins such as benzoguanamine resins available from cyanoindustry under the names Cymel 1123 and 1125 and urea resins available from cyanoindustry under the names Powderlink 1174 and 1196. In addition to being commercially available, such amine-based resins may be prepared, for example, by the reaction of acrylamide or methacrylamide copolymers with formaldehyde in an alcohol-containing solution, or alternatively by the copolymerization of N-alkoxymethacrylamide or methacrylamide with other suitable monomers. Examples of the crosslinking agent may be epoxy resins such as bisphenol a epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, alicyclic epoxy resin, and glycidylamine epoxy resin.

The resist underlayer composition may optionally contain one or more surface leveling agents (or surfactants). Such surfactants are typically nonionic, although any suitable surfactant may be used. Exemplary nonionic surfactants are those containing an alkyleneoxy linkage, such as ethyleneoxy, propyleneoxy, or a combination of ethyleneoxy and propyleneoxy linkages.

Also provided is a coated substrate comprising (a) a substrate; (b) A resist underlayer formed on the substrate from the resist underlayer composition; and (c) a photoresist layer over the resist underlayer. The coated substrate may further include a silicon-containing layer and/or an organic antireflective coating disposed over the bottom resist layer and below the photoresist layer.

The above-described compositions may be used to deposit a poly (arylene ether) coating on a patterned semiconductor device substrate, wherein the poly (arylene ether) coating has a suitable thickness, such as 10nm to 500 μm, preferably 25nm to 250 μm, and more preferably 50nm to 125 μm, although such coatings may be thicker or thinner than these ranges depending on the particular application. The composition of the present invention substantially fills, preferably fills, and more preferably completely fills, the plurality of gaps on the patterned semiconductor device substrate. An advantage of the poly (arylene ether) s of the present invention is that they planarize (form a planar layer on a patterned substrate) and fill in gaps, wherein substantially no voids, and preferably no voids, are formed.

Preferably, after coating on the surface of the patterned semiconductor device substrate, the resist underlayer composition is heated (soft baked) to remove the organic solvent present. Typically, the baking temperature is 80 ℃ to 170 ℃, although other suitable temperatures may be used. Such baking to remove residual solvent is typically performed for about 30 seconds to 10 minutes, although longer or shorter times may be suitably used. After solvent removal, a layer, film or coating of the resist underlayer on the substrate surface is obtained. Preferably, the resist underlayer is then cured to form a film. Typically, such curing is achieved by heating, such as to a temperature of ≡300 ℃, preferably ≡350 ℃ and more preferably ≡400 ℃. Such a curing step may take from 1 to 180 minutes, preferably from 10 to 120 minutes, and more preferably from 15 to 60 minutes, although other suitable times may be used. Such a curing step may be carried out in an oxygen-containing atmosphere or in an inert atmosphere, and preferably in an inert atmosphere.

Optionally, an organic antireflective layer may be disposed directly on the resist underlayer. Any suitable organic anti-reflective agent may be used. As used herein, the term "antireflective agent" refers to a moiety or material that absorbs actinic radiation at the wavelength of use. Suitable organic antireflective materials are those available from Dow electronic materials Inc. under AR ^TM Those sold by brands. The particular antireflective agent used will depend on the particular photoresist used, the fabrication process used, and other considerations that are well within the ability of those skilled in the art. In use, an organic antireflective agent is typically spin coated onto the surface of the resist underlayer, followed by heating (soft bake) to remove any residual solvent, and then curing to form an organic antireflective agent layer. Such soft bake and cure steps may be performed in a single step.

A photoresist layer is then deposited over the resist underlayer, such as by spin coating. In a preferred embodiment, the photoresist layer is deposited directly on the resist underlayer (referred to as a tri-layer process). In an alternative preferred embodiment, the photoresist layer is deposited directly on the organic anti-reflective layer (known as a four layer process). A wide variety of photoresists may be suitably used, such as those used for 193nm lithography, such as available from Dow electronic materials Inc. (Markurg, mass.) as Epic ^TM Those sold under the brand name. Suitable photoresists may be positive-developed or negative-developed resists.

Optionally, one or more barrier layers may be provided on the photoresist layer. Suitable barrier layers include top coats, top antireflective coatings (or TARC layers), and the like. Preferably, when using immersion lithography to pattern the photoresist, a topcoat layer is used. Such topcoats are well known in the art and are generally commercially available, such as OC available from Dow electronic materials Inc ^TM 2000. Those skilled in the art will recognize that when an organic antireflective layer is used underneath the photoresist layer, a TARC layer is not required.

After coating, the photoresist layer is then imaged (exposed) using patterned actinic radiation, and the exposed photoresist layer is then developed using an appropriate developer to provide a patterned photoresist layer. The photoresist is preferably patterned using immersion lithography processes well known to those skilled in the art. Next, the pattern is transferred from the photoresist layer to the underlayer by an appropriate etching technique known in the art (e.g., by plasma etching), resulting in a patterned resist underlayer in a three layer process and a patterned organic anti-reflective layer in a four layer process. If a four layer process is used, the pattern is then transferred from the organic anti-reflective layer to the resist underlayer using a suitable pattern transfer technique, such as plasma etching. Then using a suitable etching technique (e.g. O ₂ Or CF (CF) ₄ Plasma) patterning the resist underlayer. During the pattern transfer etch of the resist underlayer, any remaining patterned photoresist layer and organic antireflective layer are removed. Next, the pattern is transferred to a layer below the resist underlayer, such as by a suitable etching technique, such as by plasma etching and/or wet chemical etching, to provide a patterned semiconductor device substrate. For example, the pattern may be transferred to a semiconductor device substrate. The resist underlayer of the present invention is preferably subjected to a wet chemical etching process during pattern transfer to one or more layers below the resist underlayer. Suitable wet chemical etching chemistries include, for example, mixtures comprising ammonium hydroxide, hydrogen peroxide, and water (e.g., SC-1 cleaning solutions); a mixture comprising hydrochloric acid, hydrogen peroxide, and water (e.g., an SC-2 cleaning solution); a mixture comprising sulfuric acid, hydrogen peroxide and water; a mixture comprising phosphoric acid, hydrogen peroxide and water; a mixture comprising hydrofluoric acid and water; a mixture comprising hydrofluoric acid, phosphoric acid, and water; a mixture comprising hydrofluoric acid, nitric acid, and water; a mixture comprising tetramethylammonium hydroxide and water; etc. The patterned semiconductor device substrate is then processed according to conventional means. As used herein, the term "underlayer" refers to all removable processing layers, i.e., optional organic anti-reflective layers and resist underlayer, between a semiconductor device substrate and a photoresist layer.

According to one embodiment, the resist underlayer may also be used in a self-aligned double patterning process. In this process, the underlying resist composition described above is coated on a substrate, such as by spin coating. Any remaining organic solvent is removed and the coating is cured to form a resist underlayer. A suitable intermediate layer, such as a silicon-containing hard coat layer, is optionally coated on the resist underlayer. A suitable photoresist layer is then applied to the intermediate layer, such as by spin coating. The photoresist layer is then imaged (exposed) using patterned actinic radiation, and the exposed photoresist layer is then developed using an appropriate developer to provide a patterned photoresist layer. Next, the pattern is transferred from the photoresist layer to the intermediate layer and the resist underlayer by a suitable etching technique to expose a portion of the substrate. Typically, the photoresist is also removed during this etching step. Next, a conformal silicon-containing layer is disposed over the patterned resist underlayer and the exposed portions of the substrate. Such silicon-containing layers are typically inorganic silicon layers, such as SiON or SiO, conventionally deposited by CVD ₂ . Such conformal coatings result in a silicon-containing layer on exposed portions of the substrate surface and over the underlying pattern, i.e., such silicon-containing layer substantially covers the sides and top of the underlying pattern. Next, the silicon-containing layer is partially etched (trimmed) to expose a top surface of the patterned resist underlayer and a portion of the substrate. After this partial etching step, the pattern on the substrate contains a plurality of features, each feature containing a line or post of the resist underlayer, with the silicon-containing layer directly adjacent to the sides of each resist underlayer feature. Next, the exposed areas of the resist underlayer are removed, such as by etching, to expose the substrate surface beneath the resist underlayer pattern, and a patterned silicon-containing layer is provided on the substrate surface, wherein such patterned silicon-containing layer is doubled (i.e., twice as many lines and/or pillars) as compared to the patterned resist underlayer.

Films formed from the preferred resist underlayer composition of the present invention exhibit excellent thermal stability as measured by weight loss, as compared to conventional polyarylene polymers or oligomers prepared by diels-alder reaction of dicyclopentadiene ketone monomer and a polyacetylene substituted aromatic monomer. After heating at 450 ℃ for 1 hour, the cured film formed from the present polymer has a weight loss of ∈4%, and preferably < 4%. This cured film also has a decomposition temperature of >480 ℃ and preferably >490 ℃ as determined by 5% weight loss. Higher decomposition temperatures are desirable to accommodate the higher processing temperatures used in semiconductor device fabrication. Without wishing to be bound by any particular theory, it is believed that the addition of the additive polymer to the formulations described herein as an adhesion promoter may improve the adhesion of the poly (arylene ether) to the substrate by entangling with the poly (arylene ether) or by providing an adhesive interlayer between the poly (arylene ether) and the substrate. As a result, the preferred resist underlayer of the present invention can withstand wet chemical etching processes and chemistries as described above.

The inventive concept is further illustrated by the following examples. All compounds and reagents used herein are commercially available, except for the procedures provided below.

Examples

Matrix polymer synthesis:

example 1.Polyarylene ethers (1)

A mixture of 30.0g of 3,3' - (oxybis-1, 4-phenylene) bis (2, 4, 5-triphenylcyclopentadienone) (DPO-CPD), 18.1g of 1,3, 5-TRIS (phenylethynyl) benzene (TRIS) and 102.2g of GBL was heated at 185℃for 14 hours. The reaction was then cooled to room temperature and diluted with 21.5g GBL. The crude reaction mixture was added to 1.7L of a 1:1 mixture of isopropyl alcohol (IPA)/PGME and stirred for 30 minutes. The solids were collected by vacuum filtration and washed with a 1:1 mixture of IPA/PGME. To the solid was added 0.4L of water and the slurry was heated to 50 ℃ and stirred at 50 ℃ for 30 minutes. The warm slurry was filtered by vacuum filtration. The wet cake was dried in vacuo at 70 ℃ for 2 days to afford 34.1g of oligomer 1 in 71% yield. Analysis of oligomer 1 provided M of 3487Da _w And a PDI of 1.42.

Example 2.Polyarylene ethers (2)

Oligomer 1 (10 g) from example 1 was charged to a 100mL single neck round bottom flask equipped with reflux condenser, thermocouple and nitrogen atmosphere; GBL (20 g) is then loaded. The reaction was stirred and warmed to 145 ℃ at which point phenylacetylene (1 g) was added as a capping monomer. The reaction was kept at 145 ℃ for a total of 12 hours, at which point the reaction became clear. The blocked oligomer was isolated by precipitating the reaction mixture into an excess (200 g) of Methyl Tertiary Butyl Ether (MTBE) to give 7g of oligomer 2.

The above procedure was used for matrix polymers 3-4 and additive polymer 5.

Additive polymer synthesis

Example 3.Poly (methoxystyrene) (11)

4-Methoxystyrene (70 g) was dissolved in PGMEA (138 g), and V-601 initiator (5.88 g) was added. The resulting mixture was heated to 90 ℃ under a nitrogen blanket and heating continued overnight. After the reaction was completed, the mixture was cooled to room temperature and precipitated into a 4:1 volume/volume (v/v) mixture of 1.5L of methanol and water to give a white solid. The precipitated polymer was collected by vacuum filtration and dried in a vacuum oven for 24 hours to provide the additive polymer poly (methoxystyrene) (about 60 g) as a white solid. Determination of M by GPC relative to polystyrene standards _w And found to be 8735Da (PDI 2.2).

Example 4.Poly (acetoxystyrene) (10)

4-Acetoxystyrene (45.2 g) was dissolved in PGMEA (91.7 g), and V-601 initiator (3.2 g) was added. The resulting mixture was heated to 90 ℃ under a nitrogen blanket and heating continued overnight. After the reaction was completed, the mixture was cooled to room temperature, and precipitated into 1.5L of a 1:1 (v/v) mixture of methanol and water to obtain a white solid. The precipitated polymer was collected by vacuum filtration and dried in a vacuum oven for 24 hours to provide the additive polymer poly (acetoxystyrene) (42.5 g) as a white solid. Determination of M by GPC relative to polystyrene standards _w And (2) andit was found to be 11,703Da (PDI 2.2).

The general procedure above was for additive polymers 6-15 and 24.

Example 5.1,1' -bi-2-naphthol novolak resin (22)

1,1' -bi-2-naphthol (10.0 g) and paraformaldehyde (1.05 g) were mixed in 25mL PGME and warmed to 60℃with stirring. Methanesulfonic acid (0.34 g) was then added slowly and the reaction was heated to 120 ℃ for 16 hours. After this time, the mixture was cooled to room temperature and precipitated directly into a stirred mixture of 700mL methanol/30 mL water. The solid was collected by filtration and dried in a vacuum oven overnight to give a brown solid (8.6 g). Determination of M by GPC relative to polystyrene standards _w And found to be 4,335da (PDI 3.4).

The above procedure was used for additive polymers 16-21.

Example 6.Poly (glycidyl methacrylate) (23)

Glycidyl methacrylate (10 g) was dissolved in PGMEA (23.3 g) and V-601 initiator (0.89 g) was added. The resulting mixture was heated to 80 ℃ under a nitrogen blanket and heating continued overnight. After the reaction was completed, the mixture was cooled to room temperature and precipitated into 600mL of a 4:1 volume/volume (v/v) mixture of methanol and water to give a white solid. The precipitated polymer was collected by vacuum filtration and dried in a vacuum oven for 24 hours to give the additive polymer poly (glycidyl methacrylate) (about 9 g) as a white solid.

The above procedure was used for additive polymer 25.

Evaluation example

Additive-containing formulations

The formulation was prepared by dissolving the polymer and one or more tackifying additives in a mixture of PGMEA and benzyl benzoate (97:3) at about 4 wt% solids. The amounts of additives relative to total solids are listed in the table. The resulting solution was filtered through a 0.2 μm poly (tetrafluoroethylene) (PTFE) syringe filter.

Additive-free formulations

The formulation was prepared by dissolving the polymer in a mixture of PGMEA and benzyl benzoate (97:3) at about 4 wt% solids. The resulting solution was filtered through a 0.2 μm poly (tetrafluoroethylene) (PTFE) syringe filter.

Standard coating and cleaning

Standard coating processes of the above formulation were performed on both TiN and Si substrates. The coating process included spin coating, soft bake at 170 ℃ for 60s and hard bake at 450 ℃ for 4 minutes.

A standard cleaning solution (SC 1) was prepared by mixing 30% ammonium hydroxide, 30% hydrogen peroxide and deionized water in a ratio of 1:5:40 (w/w). Ammonium hydroxide and hydrogen peroxide were both purchased from feichi and used directly. Wafer samples coated with various films were immersed in a bath containing standard cleaning solutions at 70 ℃ with gentle agitation. The treated samples were rinsed twice with deionized water and air dried. The time before significant film delamination (visual observation) was recorded to evaluate the resistance of the SOC coating to standard cleaning solution stripping. The SOC coated Si wafer was cut to sample size and prepared in the same manner. The hatched marks are made by a stylus analog pattern. Film thickness was measured before and after treatment on non-delaminated areas with standard cleaning solutions to confirm minimal film thickness variation.

Film shrinkage measurement

The film shrinkage was calculated as the decrease in FT after soft bake to after hard bake divided by the initial FT after soft bake according to equation 1.

Equation 1:

table 1 lists the standard clean delamination times on TiN substrates for SOC formulations with adhesion promoting polymer additives compared to the comparative examples.

TABLE 1

Table 2 lists the standard clean delamination times on Si substrates for SOC formulations with adhesion promoting polymer additives as compared to the comparative examples.

TABLE 2

Table 3 lists the standard clean delamination times for modified polyphenylene formulations on TiN and Si substrates with and without the adhesion promoting polymer additives.

TABLE 3 Table 3

Film thickness shrinkage for adhesion improving formulations after hard bake compared to additives and matrix polymers is listed in table 4.

TABLE 4 Table 4

Table 5 lists the thermal degradation temperatures for adhesion improving formulations compared to additives and matrix polymers.

TABLE 5

Table 5 shows that the adhesion additive is not thermally stable at 450℃and the matrix polymer is stable at that temperature. During the hard bake at 450 ℃, the film coated with the additive itself was completely degraded. Even though the additive may degrade during a hard bake at 450 ℃, the adhesion promoter-added formulation surprisingly shows improved adhesion.

While the present disclosure has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A resist underlayer composition, comprising:

a poly (arylene ether), wherein the poly (arylene ether) comprises polymerized units of one or more first monomers having two or more cyclopentadienone moieties and one or more second monomers having an aromatic moiety and two or more alkynyl moieties,

0.1 to 30 weight percent of an additive polymer different from the poly (arylene ether), based on the total weight of solids in the composition, and

the solvent is used for the preparation of the aqueous solution,

wherein the additive polymer comprises aromatic or heteroaromatic groups,

wherein the aromatic group of the additive polymer comprises at least one protected or free functional group selected from hydroxyl, mercapto and amino groups.

2. The resist underlayer composition of claim 1, where the at least one protected or free functional group is a hydroxyl group.

3. The resist underlayer composition of claim 1 or 2, where the at least one functional group is protected by a protecting group optionally comprising-O-, -NR-, -C (=o) -or a combination thereof, where R is hydrogen or C _1-10 An alkyl group.

4. The resist underlayer composition of claim 3, where the protecting group comprises formyl, substituted or unsubstituted straight or branched C _1-10 Alkyl, substituted or unsubstituted C _3-10 Cycloalkyl, substituted or unsubstituted C _2-10 Alkenyl, substituted or unsubstituted C _2-10 Alkynyl groups or combinations thereofWherein R is hydrogen or C _1-10 An alkyl group.

5. The resist underlayer composition of claim 1, where the additive polymer comprises a structural unit represented by formula (I):

wherein, in the formula (I),

ar is C _6-40 Aromatic organic radicals or C _3-40 Heteroaromatic organic groups;

x and R ₁ To R ₃ Each independently is hydrogen, substituted or unsubstituted C _1-10 Alkyl, substituted or unsubstituted C _2-10 Alkenyl, substituted or unsubstituted C _2-10 Alkynyl, substituted or unsubstituted C _3-10 Cycloalkyl, or substituted or unsubstituted C _6-20 An aryl group;

y is OR ₄ 、SR ₅ 、NR ₆ R ₇ Or CR (CR) ₈ R ₉ OR ₄ Wherein R is ₄ To R ₉ Each independently is hydrogen, formyl, substituted or unsubstituted C _1-5 Alkyl, substituted or unsubstituted C _2-5 Alkenyl, substituted or unsubstituted C _2-5 Alkynyl, or substituted or unsubstituted C _3-8 Cycloalkyl groups, each optionally comprising-O-, -NR-, -C (=o) -or a combination thereof, wherein R is hydrogen or C _1-10 Alkyl, wherein R is ₆ And R is ₇ Optionally linked to form a ring, and wherein R ₈ And R is ₉ Optionally linked to form a ring;

l is a single bond or a divalent linking group; and

m and n are each independently integers of 1 to 20, provided that the sum of m and n does not exceed the total number of atoms of Ar which may be substituted with X and Y.

6. The resist underlayer composition of claim 1, where the additive polymer comprises a structural unit represented by formula (II):

wherein, in the formula (II),

X、R ₁ and R is ₂ Each independently is hydrogen, substituted or unsubstituted C _1-10 Alkyl, substituted or unsubstituted C _2-10 Alkenyl, substituted or unsubstituted C _2-10 Alkynyl, substituted or unsubstituted C _3-10 Cycloalkyl, or substituted or unsubstituted C _6-20 An aryl group;

y is OR ₄ 、SR ₅ 、NR ₆ R ₇ Or CR (CR) ₈ R ₉ OR ₄ Wherein R is ₄ To R ₉ Each independently is hydrogen, formyl, substituted or unsubstituted C _1-5 Alkyl, substituted or unsubstituted C _2-5 Alkenyl, substituted or unsubstituted C _2-5 Alkynyl, or substituted or unsubstituted C _3-8 Cycloalkyl groups, each optionally comprising-O-, -NR-, -C (=o) -or a combination thereof, wherein R is hydrogen or C _1-10 Alkyl, wherein R is ₆ And R is ₇ Optionally linked to form a ring, and wherein R ₈ And R is ₉ Optionally linked to form a ring; and

7. The resist underlayer composition of claim 1, where the additive polymer comprises a structural unit represented by formula (III):

wherein, in the formula (III),

x is hydrogen, substituted or unsubstituted C _1-10 Alkyl, substituted or unsubstituted C _2-10 Alkenyl, substituted or unsubstituted C _2-10 Alkynyl, substituted or unsubstituted C _3-10 Cycloalkyl, or substituted or unsubstituted C _6-20 An aryl group;

8. The resist underlayer composition of claim 1, where the amount of additive polymer is 0.1 to 20 weight percent, based on the total weight of solids in the composition.

9. A method of forming a pattern, the method comprising: (a) Coating a layer of the resist underlayer composition of any one of claims 1 to 8 on a substrate; (b) Curing the applied resist underlayer composition to form a resist underlayer; (c) forming a photoresist layer over the resist underlayer.

10. The method of claim 9, further comprising forming a silicon-containing layer and/or an organic anti-reflective coating on the resist underlayer prior to forming the photoresist layer.

11. The method of claim 9 or 10, further comprising patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the resist underlayer and a layer below the resist underlayer.

12. The method of claim 11, wherein transferring the pattern comprises a wet chemical etching process.